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L. Chacun-Lefevre et al. / Tetrahedron 58 (2002) 10181–10188
10186
prepared from 4 in 99% yield as a white solid. Mp 157–
1588C (EtOAc/petroleum ether); IR (KBr) n 3420 (NH),
3257 (NH), 1636 (CO) cm21; 1H NMR (250 MHz, CDCl3)
d 2.41 (q, 2H, CH2, J¼6.8 Hz), 3.58 (q, 2H, CH2,
J¼6.8 Hz), 5.16 (dd, 1H, vCH2, J¼1.7, 10.0 Hz), 5.26
(dd, 1H, vCH2, J¼1.0, 18.5 Hz), 5.80–5.87 (m, 1H,
vCH), 6.36 (br s, 1H, NH), 6.80 (d, 1H, Har, J¼1.2 Hz),
7.14 (t, 1H, Har, J¼8.0 Hz), 7.30 (t, 1H, Har, J¼8.0 Hz),
7.45 (d, 1H, Har, J¼8.0 Hz), 7.64 (d, 1H, Har, J¼8.0 Hz),
9.42 (br s, 1H, NH); 13C NMR (62,90 MHz, CDCl3) d 34.2
(CH2), 38.9 (CH2), 102.0 (CH), 112.5 (CH), 118.0 (CH2),
121.0 (CH), 122.2 (CH), 124.8 (CH), 128.0 (C), 131.2 (C),
135.5 (CH), 136.8 (C), 162.1 (CO); MS m/z 215 (MþH)þ;
Anal. calcd for C13H14N2O: C, 72.87; H, 6.59; N, 13.07.
Found: C, 72.65; H, 6.45; N, 13.22.
CH2), 4.08–4.14 (m, 1H, CH2), 5.14 (dd, 1H, CH2, J¼1.7,
11.2 Hz), 5.17 (dd, 1H, CH2, J¼1.7, 17.2 Hz), 5.39 (dd, 1H,
CH2, J¼1.2, 11.5 Hz), 5.78 (dd, 1H, CH2, J¼1.2, 17.7 Hz),
5.81–6.02 (m, 1H, CHv), 6.57–6.64 (m, 1H, CHv),
7.27–7.36 (m, 2H, Har), 7.79 (d, 1H, Har, J¼7.7 Hz), 8.15
(d, 1H, Har, J¼7.7 Hz); 13C NMR (62.90 MHz, CDCl3) d
27.5 (3CH3), 28.1 (3CH3), 32.8 (CH2), 43.9 (CH2), 83.3 (C),
84.8 (C), 115.6 (CH), 116.4 (C), 117.0 (CH2), 117.1 (CH2),
120.6 (CH), 123.5 (CH), 125.5 (CH), 126.6 (CH), 127.5 (C),
132.3 (C), 135.2 (CH), 135.3 (C), 149.0 (CO), 152.0 (CO),
162.3 (CO); MS m/z 441 (MþH)þ; Anal. calcd for
C25H32N2O5: C, 68.16; H, 7.32; N, 6.36. Found: C, 68.47;
H, 7.21; N, 6.25.
4.1.15. tert-Butyl 2-{[((Z)-6-[(tert-butoxycarbonyl)[(3-
vinyl-1H-indol-2-yl)carbonyl]amino-3-hexenyl)amino]
carbonyl}-3-vinyl-1H-indole-1-carboxylate (16). Grubb’s
catalyst (25 mg, 0.03 mmol) was added, under nitrogen, to a
solution of 15 (120 mg, 0.27 mmol) in dichloromethane
(6 mL). The final solution was stirred at room temperature
for 48 h. After evaporation of the solvent, the residue was
purified by column chromatography on silica gel (eluent:
petroleum ether/EtOAc 95:5) to afford 16 (58 mg, 50%) as a
colorless gum. IR (film) n 1755 (CO), 1732 (CO), 1672
3-Formyl-1H-indole-2-carboxylic acid (but-3-enyl)amide.
According to the procedure for the synthesis of 11, the
aldehyde was prepared from 1H-indole-2-carboxylic acid
(but-3-enyl)amide in 76% yield as a solid. Mp 173–1748C
(EtOAc/petroleum ether); IR (KBr) n 3364 (NH), 3258
(NH), 2710 (CHO), 1695 (CHO), 1634 (CO) cm21 1H
;
NMR (250 MHz, CDCl3) d 2.52 (q, 2H, CH2, J¼6.7 Hz),
3.60 (q, 2H, CH2, J¼6.2 Hz), 5.15 (dd, 1H, vCH2, J¼1.7,
11.7 Hz), 5.21 (dd, 1H, vCH2, J¼1.7, 17.2 Hz), 5.82–6.01
(m, 1H, vCH), 7.34–7.64 (m, 2H, Har), 7.65 (d, 1H, Har,
J¼8.0 Hz), 8.03 (d, 1H, Har, J¼8.0 Hz), 10.34 (s, 1H,
CHO), 11.01 (br s, 1H, NH), 11.49 (br s, 1H, NH); 13C NMR
(62.90 MHz, CDCl3) d 33.9 (CH2), 36.0 (CH2), 113.1 (C),
114.0 (CH), 117.6 (CH2), 118.6 (CH), 123.9 (CH), 125.7
(CH), 129.7 (C), 135,3 (CH), 135.4 (C), 135.5 (C), 160.1
(CO), 185.9 (CHO); MS m/z 243 (MþH)þ; Anal. calcd for
C14H14N2O2: C, 69.41; H, 5.82; N, 11.56. Found: C, 69.60;
H, 5.93; N, 11.39.
1
(CO) cm21; H NMR (250 MHz, CDCl3) d 1.09 (s, 18H,
C(CH3)3), 1.61 (s, 18H, C(CH3)3), 2.48–2.62 (m, 4H, CH2),
3.73–3.84 (m, 2H, CH2), 4.02–4.16 (m, 2H, CH2), 5.40 (dt,
2H, CH2, J¼1.2, 11.2 Hz), 5.60–5.67 (m, 2H, CHv), 5.78
(dd, 2H, CH2, J¼1.2, 17.9 Hz), 6.56–6.70 (m, 2H, CHv),
7.24–7.36 (m, 4H, Har), 7.80 (d, 2H, Har, J¼7.7 Hz), 8.15
(d, 2H, Har, J¼7.7 Hz); 13C NMR (62.90 MHz, CDCl3) d
27.6 (6CH3), 28.2 (6CH3), 31.7 (2CH2), 44.0 (2CH2), 83.4
(2C), 84.9 (2C), 115.7 (2CH), 116.4 (2C), 117.2 (2CH2),
120.6 (2CH), 123.5 (2CH), 125.5 (2CH), 126.7 (2CH),
127.6 (2C), 128.4 (2CH), 129.3 (2C), 132.4 (2C), 149.1
(2CO), 152.0 (2CO), 164.4 (2CO); MS m/z 854 (MþH)þ;
Anal. calcd for C48H60N4O10: C, 67.59; H, 7.09; N, 6.57.
Found: C, 67.33; H, 7.24; N, 6.48.
3-Vinyl-1H-indole-2-carboxylic acid (but-3-enyl)amide.
According to the procedure for the synthesis of 12, the
vinyl derivative was prepared from 3-formyl-1H-indole-2-
carboxylic acid (but-3-enyl)amide in quantitative yield as a
solid. Mp 97–988C (EtOAc/petroleum ether); IR (KBr) n
4.1.16. N-Allyl 1-allyl-1H-indole-2-carboxamide (18). A
suspension of potassium carbonate (553 mg, 4.00 mmol),
allyl bromide (208 mL, 2.40 mmol) and compound 10
(200 mg, 1.00 mmol) in acetonitrile (10 mL) was refluxed
for 24 h. After evaporation of the solvent, the residue was
dissolved in ethyl acetate (10 mL) and washed twice with
water. The organic layer was dried over MgSO4 and
evaporated in vacuo. The residue was purified by column
chromatography on silica gel (eluent: petroleum ether/
EtOAc 8:2) to afford 19 (50 mg, 25%) then 18 (120 mg,
60%) as white solids. Mp 92–938C (EtOAc/petroleum
3410 (NH), 3258 (NH), 1636 (CO) cm21 1H NMR
;
(250 MHz, CDCl3) d 2.40 (q, 2H, CH2, J¼6.7 Hz), 3.60
(q, 2H, CH2, J¼6.2 Hz), 5.14–5.22 (m, 2H, vCH2), 5.64
(dd, 1H, vCH2, J¼1.7, 11.2 Hz), 5.77–5.86 (m, 2H,
vCH2, vCH), 6.44 (s, 1H, NH), 6.96–7.08 (m, 1H, vCH),
7.17 (td, 1H, Har, J¼1.0, 8.2 Hz), 7.30 (td, 1H. Har, J¼1.0,
8.2 Hz), 7.42 (d, 1H, Har, J¼8.2 Hz), 7.77 (d, 1H, Har,
J¼8.2 Hz), 9.40 (br s, 1H, NH); 13C NMR (62.90 MHz,
CDCl3) d 33.8 (CH2), 39.0 (CH2), 112.1 (CH), 115.3 (C),
117.8 (CH), 120.2 (CH). 120.8 (CH2), 120.9 (CH2), 124.8
(CH), 126.9 (C), 127.5 (C), 128.7 (CH), 135.3 (CH), 135.7
(C), 162.3 (CO); MS m/z 241 (MþH)þ. Anal. calcd for
C15H16N2O: C, 74.97; H, 6.71; N, 11.66. Found: C, 74.65;
H, 6.87; N, 11.79.
1
ether); IR (KBr) n 3242 (NH), 1625 (CO) cm21; H NMR
(250 MHz, CDCl3) d 4.07–4.12 (m, 2H, CH2), 4.97 (dd, 1H,
vCH2, J¼1.2, 17.2 Hz), 5.14 (dd, 1H, vCH2, J¼1.2,
10.2 Hz), 5.20–5.35 (m, 4H, vCH), 5.90–6.11 (m, 2H,
vCH), 6.57 (br s, 1H, NH), 6.94 (s, 1H, Har), 7.17–7.23 (m,
1H, Har), 7.30–7.43 (m, 2H, Har), 7.66 (d, 1H, Har,
J¼7.8 Hz); 13C NMR (62.90 MHz, CDCl3) d 41.9 (CH2),
46.8 (CH2), 104.4 (CH), 110.7 (CH), 116.0 (CH2), 116.5
(CH2), 120.6 (CH), 121.9 (CH), 124.2 (CH), 126.2 (C),
131.5 (C), 134.1 (CH), 134.2 (CH), 138.5 (C), 162.3
(CO); MS m/z 241 (MþH)þ; Anal. calcd for C15H16N2O:
C, 74.97; H, 6.71; N, 11.66. Found: C, 75.27; H, 6.62; N,
11.79.
tert-Butyl 2-{[(but-3-enyl-tert-butoxycarbonyl)amino] car-
bonyl}-3-vinyl-1H-indole-1-carboxylate (15). According to
the procedure for the synthesis of 5 from 12, compound 15
was prepared from 3-vinyl-1H-indole-2-carboxylic acid
(but-3-enyl)amide in 98% yield as a gum. IR (film) n
;
1748 (CO), 1740 (CO), 1680 (CO) cm21 1H NMR
(250 MHz, CDCl3) d 1.07 (s, 9H, C(CH3)3), 1.61 (s, 9H,
C(CH3)3), 2.49 (q, 2H, CH2, J¼6.8 Hz), 3.82–3.88 (m, 1H,